EP2892990B1 - Detergent or cleaning agent with an improved enzyme performance - Google Patents

Description

1. a) mindestens eine Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO. 1 angegebenen Aminosäuresequenz über deren Gesamtlänge zu mindestens 95% identisch ist und in der Zählung gemäß SEQ ID NO. 1 an Position 99 die Aminosäure Glutaminsäure (E) aufweist;
2. b) 4-Formylphenylboronsäure
3. c) mindestens ein weiteres von der Protease a) verschiendenes Enzym aus der Gruppe der Amylasen, und
4. d) mindestens ein organisches Lösungsmittel, wobei der Gewichtsanteil des mindestens einen organischen Lösungsmittels am Gesamtgewicht des Reinigungsmittels 0,5 bis 5,0 Gew.-% beträgt.

The application relates to enzyme-containing detergents and cleaning processes using these agents. This application relates in particular to cleaning agents which contain specific proteases in combination with 4-formylphenylboronic acid and at least one further enzyme and to purification processes in the course of which these agents are used.
Detergents, in particular detergents for automatic dishwashing and textile cleaning, generally contain, in addition to the builders and surfactants, one or more enzymes as further active ingredient active in cleaning. Typical cleaning-active enzymes are the proteases, the amylases and lipases and cellulases.
A disadvantage of prior art protease and amylase-containing cleaners is their inadequate storage stability and their lack of amylolytic activity. Often, the presence of protease results in the loss of amylolytic activity as the protease inactivates the amylase. The washing or cleaning agent then no longer shows optimal cleaning performance. The object of the present application is to overcome the mentioned disadvantage and to provide protease- and amylase-containing cleaning agents which are sufficiently storage-stable and have improved amylolytic activity.
It has surprisingly been found that detergents which contain specific proteases in combination with 4-formylphenylboronic acid and at least one further enzyme have improved cleaning performance compared with detergents based on conventional proteases. The 4-formylphenylboronic acid is a protease inhibitor known in the art, its inhibitory activity in the granted European patent EP 832 174 B1 (Novozymes) is described. Detergents containing protease, amylase and 4-formylphenylboronic acid are disclosed, for example, in International Applications WO 2010/034736 A1 (Unilever) and WO2010 / 092066 (Henkel AG & Co. KGaA). WO2012 / 080202 (Henkel AG & Co. KGaA) discloses a liquid detergent composition containing a protease mutant from B. lentus in combination with an amylase, wherein the composition is sufficiently storage stable and has improved amylase activity. A first subject of the present application is therefore a detergent containing

1. a) at least one protease which comprises an amino acid sequence which corresponds to the amino acid sequence shown in SEQ ID NO. 1 amino acid sequence is at least 95% identical over the entire length and in the count according to SEQ ID NO. 1 at position 99 has the amino acid glutamic acid (E);
2. b) 4-formylphenylboronic acid
3. c) at least one further enzyme belonging to the protease a) from the group of amylases, and
4. d) at least one organic solvent, wherein the weight fraction of the at least one organic solvent in the total weight of the cleaning agent is 0.5 to 5.0 wt .-%.

Detergents according to the invention which contain the abovementioned combination of a specific protease with 4-formylphenylboronic acid and a further enzyme are not only storage-stable, but are distinguished by a higher protease content (based on active enzyme) but different protease compared to prior art detergents enzymatic cleaning power of the further enzyme c).

A first essential component of inventive cleaning agents is the protease a).

The protease a) preferably comprises an amino acid sequence which corresponds to the amino acid sequence shown in SEQ ID NO. 1 is at least 95% and more preferably at least 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5% and 99% identical over its entire length, and in the count according to SEQ ID NO. 1 at position 99 has the amino acid glutamic acid (E). A particularly preferred protease in this regard is shown in SEQ ID NO. 3 indicated.

Further preferred proteases are proteases as described above, which are furthermore located at position 211 in the counting according to SEQ ID NO. 1 have the amino acid leucine (L).

SEQ ID NO. Figure 1 is the sequence of the mature (mature) alkaline protease from Bacillus lentus DSM 5483, which is disclosed in the international patent application WO 92/21760 , and the disclosure of which is hereby incorporated by reference. SEQ ID NO. Figure 2 is the sequence of the mature (mature) protease subtilisin 309 from Bacillus lentus.

Particularly preferred cleaning agents according to the invention are characterized in that the protease a) comprises an amino acid sequence which corresponds to the amino acid sequence shown in SEQ ID NO. 1 amino acid sequence is identical to at least 99% over the entire length and in the count according to SEQ ID NO. 1 at position 99 in the amino acid glutamic acid (E). Most preferably, the protease a) has an amino acid sequence which in the count according to SEQ ID NO. 1 in positions 1-98 and 100-269 SEQ ID NO. 1 corresponds to and Position 99 has the amino acid glutamic acid (E). Such a protease is shown in SEQ ID NO. 3 indicated.

The identity of nucleic acid or amino acid sequences is determined by a sequence comparison. This sequence comparison is based on the BLAST algorithm established in the prior art and commonly used (cf., for example, US Pat Altschul, SF, Gish, W., Miller, W., Myers, EW & Lipman, DJ (1990) "Basic local alignment search tool." J. Mol. Biol. 215: 403-410 , and Altschul, Stephan F., Thomas L. Madden, Alejandro A. Schaffer, Jinghui Zhang, Hheng Zhang, Webb Miller, and David J. Lipman (1997): "Gapped BLAST and PSI-BLAST: a new generation of protein database search programs "; Nucleic Acids Res., 25, pp.3389-3402 ) and happens in principle in that similar sequences of nucleotides or amino acids in the Nucleic acid or amino acid sequences are assigned to each other. A tabular assignment of the respective positions is referred to as alignment. Another algorithm available in the prior art is the FASTA algorithm. Sequence comparisons (alignments), in particular multiple sequence comparisons, are created with computer programs. Frequently used, for example, the Clustal series (see, for example Chenna et al. (2003): Multiple sequence alignment with the Clustal series of programs. Nucleic Acid Research 31, 3497-3500 ), T-Coffee (cf., for example Notredame et al. (2000): T-Coffee: A novel method for multiple sequence alignments. J. Mol. Biol. 302, 205-217 ) or programs based on these programs or algorithms. In the present patent application, all alignment comparisons (alignments) were made using the Vector NTI® Suite 10.3 computer program (Invitrogen Corporation, 1600 Faraday Avenue, Carlsbad, California, USA) with the default default parameters whose AlignX module for sequence comparisons is based on ClustalW ,

Such a comparison also allows a statement about the similarity of the compared sequences to each other. It is usually given in percent identity, that is, the proportion of identical nucleotides or amino acid residues at the same or in an alignment corresponding positions. The broader concept of homology involves conserved amino acid substitutions in the consideration of amino acid sequences, that is, amino acids with similar chemical activity, as these usually perform similar chemical activities within the protein. Therefore, the similarity of the sequences compared may also be stated as percent homology or percent similarity. Identity and / or homology information can be made about whole polypeptides or genes or only over individual regions. Homologous or identical regions of different nucleic acid or amino acid sequences are therefore defined by matches in the sequences. Such areas often have identical functions. They can be small and comprise only a few nucleotides or amino acids. Often, such small regions exert essential functions for the overall activity of the protein. It may therefore be useful to relate sequence matches only to individual, possibly small areas. Unless otherwise indicated, identity or homology information in the present application, however, refers to the total length of the particular nucleic acid or amino acid sequence indicated.

The active protein-based weight fraction of the protease a) in the total weight of cleaning agents preferred according to the invention is preferably 0.005 to 1.0% by weight, preferably 0.01 to 0.5% by weight and in particular 0.02 to 0.2% by weight. -%. The protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method ( Gornall AG, CS Bardawill and MM David, J. Biol. Chem., 177 (1948), pp. 751-766 ). The determination of the active protein concentration was in this respect via a titration of the active sites using a suitable irreversible inhibitor (for proteases, for example Phenylmethylsulfonyl fluoride (PMSF)) and determination of the residual activity (cf. Bender, M., et al., J. Am. Chem. Soc. 88, 24 (1966), p. 5890-5913 ).

The cleaning agents according to the invention contain as the second essential constituent 4-formylphenylboronic acid (4-FPBA). The proportion by weight of 4-formylphenylboronic acid in the total weight of the cleaning agent is preferably from 0.0005 to 2.0 wt .-%, preferably 0.001 to 1.0 wt .-% and in particular 0.01 to 0.1 wt .-%.

The cleaning agents according to the invention contain as further essential component c) at least one further enzyme. For example, lipases or cutinases can be used as enzyme c), in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed, in particular those with the amino acid exchange D96L. These include, for example, the lipases which are obtainable or further developed from Humicola lanuginosa ( Thermomyces lanuginosus ), in particular those having one or more of the following amino acid exchanges starting from said lipase in positions D96L, T213R and / or N233R, particularly preferably T213R and N233R. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens . It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii .

The agents according to the invention may also contain cellulases or hemicellulases such as mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases or β-glucanases.

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

With particular preference the detergents according to the invention contain as enzyme c) at least one amylase. An amylase is an enzyme as described in the introduction. For amylases, synonymous terms may be used, for example, 1,4-alpha-D-glucan glucanohydrolase or glycogenase. Amylases preferred according to the invention are .alpha.-amylases. Crucial for determining whether an enzyme is an α-amylase according to the invention is its ability to hydrolyze a (1-4) -glycoside bonds in the amylose of the starch.

Exemplary amylases are the α-amylases from Bacillus licheniformis, from Bacillus amyloliquefaciens or from Bacillus stearothermophilus, and in particular also their further developments improved for use in detergents or cleaners. The enzyme from Bacillus licheniformis is available from the company Novozymes under the name Termamyl® and from the company Danisco / Genencor under the name Purastar®ST. Further development products of this α-amylase are available from the company Novozymes under the trade name Duramyl® and Termamyl®ultra, from the company Danisco / Genencor under the name Purastar®OxAm and from the company Daiwa Seiko Inc., Tokyo, Japan, as Keistase®. The Bacillus amyloliquefaciens α-amylase is sold by the company Novozymes under the name BAN®, and variants derived from the Bacillus stearothermophilus α-amylase under the names BSG® and Novamyl®, also from the company Novozymes. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from Bacillus agaradherens (DSM 9948). Likewise, fusion products of all the molecules mentioned can be used. In addition, the further developments of the α-amylase from Aspergillus niger and A. oryzae available under the trade name Fungamyl® from the company Novozymes are suitable. Further advantageously usable commercial products are, for example, the amylase-LT® and Stainzyme® or Stainzyme ultra® or Stainzyme plus®, the latter also from the company Novozymes. Also variants of these enzymes obtainable by point mutations can be used according to the invention. Particularly preferred amylases are disclosed in International Publications WO 00/60060 . WO 03/002711 . WO 03/054177 and WO07 / 079938 , whose disclosure is therefore expressly referred to, or whose disclosure in this regard is therefore expressly incorporated into the present patent application.

In summary, preferred cleaning agents according to the invention are characterized in that as further enzyme c) at least one enzyme from the group of amylases, cellulases, hemicellulases, mannanases, tannases, xylanases, xanthanases, xyloglucanases, β-glucosidases, pectinases, carrageenases, perhydrolases, oxidases, oxidoreductases or a lipase, and mixtures thereof, preferably from the group of amylases. The active protein-based proportion by weight of the enzyme c) in the total weight of preferred cleaning agent is preferably 0.0005 to 1.0 wt .-%, preferably 0.001 to 0.5 wt .-% and in particular 0.002 to 0.2 wt .-%.

The cleaning agents may in addition to the ingredients described above contain cleaning active substances, with substances from the group of surfactants, builders, polymers, glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers are preferred. These preferred ingredients will be described in more detail below.

• R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• A, A', A" und A'" unabhängig voneinander für einen Rest aus der Gruppe -CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-, -CH₂-CH(CH₂-CH₃) stehen,
• w, x, y und z für Werte zwischen 0,5 und 120 stehen, wobei x, y und/oder z auch 0 sein können bevorzugt sind.

A preferred constituent of the cleaning agents according to the invention are the nonionic surfactants, nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A ''' O) _z -R ² , in the

• R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ),
• w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0 are preferred.

By the addition of the aforementioned nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A '''O) _z -R ² , hereinafter also referred to as "hydroxy mixed ethers", surprisingly, the cleaning performance of inventive enzyme-containing preparations can be significantly improved both in comparison to surfactant-free system as well as compared to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated Contain fatty alcohols.

The use of these nonionic surfactants having one or more free hydroxyl groups on one or both terminal alkyl radicals can markedly improve the stability of the enzymes present in the washing or cleaning agent preparations according to the invention.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

Particularly preferred are surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15.
The group of these non-ionic surfactants include, for example, the C _2-26 fatty alcohol (PO) ₁ - (EO) _15-40 2-hydroxyalkyl ethers, in particular the C _8-10 fatty alcohol (PO) ₁ - (EO) ₂₂ -2 -hydroxydecylether.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² independently of one another is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2 Butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. When the value x ≥ 2, each R ³ in the above formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{2 may be} different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the rest
R ³ is H, -CH ₃ or -CH ₂ CH ₃ particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1 such that the above formula is R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH ) CH ₂ OR ² simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

• R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• A für einen Rest aus der Gruppe CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃) steht, und
• w für Werte zwischen 1 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht
  Zur Gruppe dieser nichtionischen Tenside zählen beispielsweise die C_4-22 Fettalkohol-(EO)_10-80-2-hydroxyalkylether, insbesondere auch die C_8-12 Fettalkohol-(EO)₂₂-2-hydroxydecylether und die C_4-22 Fettalkohol-(EO)_40-80-2-hydroxyalkylether

Finally, the nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ^{2 have} proved to be particularly effective, in which

• R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A is a radical from the group CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), and
• w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40
  The group of these nonionic surfactants include, for example, the C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ethers, in particular also the C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ethers and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ether

Preferred cleaning agents are characterized in that the cleaning agent contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, wherein the weight fraction of the nonionic surfactant in the total weight of the cleaning agent is preferably 0.2 to 10 wt .-%, preferably 0, 4 to 7.0 wt .-% and in particular 0.6 to 6.0 wt .-% is.

Preferred cleaning agents according to the invention for use in automatic dishwashing processes comprise, in addition to the nonionic surfactants described above, further surfactants, in particular amphoteric surfactants. However, the proportion of anionic surfactants in the total weight of these detergents is preferably limited. Thus, preferred automatic dishwashing detergents are characterized in that, based on their total weight, they contain less than 5.0% by weight, preferably less than 3.0% by weight, particularly preferably less than 2.0% by weight of anionic surfactant. The use of anionic surfactants in larger quantities is thereby omitted, in particular to avoid excessive foaming.

Another preferred ingredient of detergents according to the invention are complexing agents. Particularly preferred complexing agents are the phosphonates. The complex-forming phosphonates include, in addition to the 1-hydroxyethane-1,1-diphosphonic a variety of different Compounds such as diethylenetriamine penta (methylenephosphonic acid) (DTPMP). Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

1. a) Aminotrimethylenphosphonsäure (ATMP) und/oder deren Salze;
2. b) Ethylendiamintetra(methylenphosphonsäure) (EDTMP) und/oder deren Salze;
3. c) Diethylentriaminpenta(methylenphosphonsäure) (DTPMP) und/oder deren Salze;
4. d) 1-Hydroxyethan-1,1-diphosphonsäure (HEDP) und/oder deren Salze;
5. e) 2-Phosphonobutan-1,2,4-tricarbonsäure (PBTC) und/oder deren Salze;
6. f) Hexamethylendiamintetra(methylenphosphonsäure) (HDTMP) und/oder deren Salze;
7. g) Nitrilotri(methylenphosphonsäure) (NTMP) und/oder deren Salze.

Eie in the context of this application preferred cleaning agent contains one or more phosphonate (s) from the group

1. a) aminotrimethylenephosphonic acid (ATMP) and / or salts thereof;
2. b) ethylenediaminetetra (methylenephosphonic acid) (EDTMP) and / or salts thereof;
3. c) diethylenetriamine penta (methylenephosphonic acid) (DTPMP) and / or salts thereof;
4. d) 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and / or salts thereof;
5. e) 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and / or salts thereof;
6. f) hexamethylenediaminetetra (methylenephosphonic acid) (HDTMP) and / or salts thereof;
7. g) nitrilotri (methylenephosphonic acid) (NTMP) and / or salts thereof.

Particularly preferred are cleaning agents which contain as phosphonates 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP). Of course, the cleaning agents according to the invention may contain two or more different phosphonates. Preferred cleaning agents according to the invention are characterized in that the cleaning agent contains at least one complexing agent from the group of the phosphonates, preferably 1-hydroxyethane-1,1-diphosphonate, wherein the weight fraction of the phosphonate in the total weight of the cleaning agent is preferably 0.1 and 8.0 wt .-%, preferably 0.2 and 5.0 wt .-% and in particular 0.5 and 3.0 wt .-% is.

The cleaning agents according to the invention preferably further comprise builder. The builders include, in particular, the silicates, carbonates, organic co-builders and, where there are no ecological prejudices against their use, also the phosphates.

Among the large number of commercially available phosphates, the alkali metal phosphates, with particular preference of pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) or pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), have the greatest importance for the agents according to the invention. If phosphates are used as cleaning-active substances in the cleaning agent in the context of the present application, preferred agents comprise this phosphate (s), preferably pentakalium triphosphate, wherein the weight fraction of the phosphate in the total weight of the cleaning agent is preferably 5.0 and 40% by weight. , preferably 10 and 30 wt .-% and in particular 12 and 25 wt .-% is.

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. These classes of substances are described below.

Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here. The citric acid or salts of citric acid are used with particular preference as builder substance. Another particularly preferred builder substance is methylglycine diacid (MGDA).

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The against polystyrenesulfonic acids measured molar masses are generally much higher than the molecular weights specified in this document.

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates.

To improve the cleaning performance and / or to adjust the viscosity, preferred cleaning agents comprise at least one hydrophobically modified polymer, preferably a hydrophobically modified carboxylic acid group-containing polymer, wherein the weight fraction of the hydrophobically modified polymer in the total weight of the cleaning agent is preferably 0.1 to 10% by weight. , preferably between 0.2 and 8.0 wt .-% and in particular 0.4 to 6.0 wt .-% is.

In addition to the builders described above, detergent-active polymers may be included in the detergent. The proportion by weight of cleaning-active polymers in the total weight of mechanical cleaning agents according to the invention is preferably from 0.1 to 20% by weight, preferably from 1.0 to 15% by weight and in particular from 2.0 to 12% by weight.

As cleaning-active polymers are preferably used sulfonic acid-containing polymers, in particular from the group of copolymeric polysulfonates. These copolymeric polysulfonates contain, in addition to sulfonic acid-containing (s) monomer (s) at least one monomer from the group of unsaturated carboxylic acids.

As unsaturated carboxylic acid (s), it is particularly preferred to use unsaturated carboxylic acids of the formula R ¹ (R ² ) C =C (R ³ ) COOH in which R ¹ to R ³ independently of one another represent -H, - CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.

In the case of the monomers containing sulfonic acid groups, preference is given to those of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H in which R ⁵ to R ⁷ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH or -COOH or -COOR ⁴ wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO - (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas H ₂ C =CH-X-SO ₃ H, H ₂ C =C (CH ₃ ) -X-SO ₃ H and HO ₃ SX- (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, - C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts.

In the polymers, the sulfonic acid groups may be wholly or partly in neutralized form. The use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred automatic dishwashing agents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

In a further preferred embodiment, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer in addition to carboxyl-containing monomer and sulfonic acid-containing monomer. The use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.

1. i) Carbonsäuregruppen-haltige Monomer(e)
2. ii) Sulfonsäuregruppen-haltige Monomer(e)
3. iii) nichtionische Monomer(e).

werden erfindungsgemäß bevorzugt. Durch den Einsatz dieser Terpolymere konnte die Klarspülleistung erfindungsgemäßer maschineller Geschirrspülmittel gegenüber vergleichbaren Geschirrspülmitteln, die Sulfopolymere ohne Zusatz nichtionischer Monomere enthalten, verbessert werden.A detergent containing a copolymer comprising

1. i) carboxylic acid group-containing monomer (s)
2. ii) sulfonic acid group-containing monomer (s)
3. iii) nonionic monomer (s).

are preferred according to the invention. The use of these terpolymers has improved the rinse performance of automatic dishwashing agents according to the invention compared to comparable dishwashing detergents which contain sulfopolymers without the addition of nonionic monomers.

The nonionic monomers used are preferably monomers of the general formula R ¹ (R ² ) C =C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X represents an optionally present spacer group selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 represents} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or represents an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, α-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-α-olefin, 2-styrene, α Methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N- (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N - (2-ethylhexyl) acrylamide, octyl acrylate, Methacrylsäureoctylester, N - (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N - (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, N - (stearyl) acrylamide, behenyl acrylate, Methacrylsäurebehenylester and N - (behenyl) acrylamide or mixtures thereof.

The proportion by weight of the sulfonic acid-containing copolymers in the total weight of inventive detergents is preferably 0.1 to 15 wt .-%, preferably 1.0 to 12 wt .-% and in particular 2.0 to 10 wt .-%.

The cleaning agents according to the invention can be present in the ready-to-use forms known to the person skilled in the art, ie for example in solid or liquid form but also as a combination of solid and liquid forms. Powder, granules, extrudates or compactates, in particular tablets, are particularly suitable as firm supply forms. The liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels.

The cleaning agents according to the invention are preferably in liquid form. Based on their total weight, preferred cleaners contain more than 40% by weight, preferably between 50 and 90% by weight and in particular between 60 and 80% by weight of water.

As a further component, the cleaning agents according to the invention contain an organic solvent. The addition of organic solvents has an advantageous effect on the enzyme stability and the cleaning performance of these agents. Preferred organic solvents are selected from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers. Preferably, the solvents are selected from ethanol, n- or i-propanol, butanol, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, Etheylenglykolmonon-butyl ether, diethylene glycol methyl ether, di-ethylenglykolethylether , Propylenglykolmethyl-, ethyl or propyl ether, Dipropylenglykolmethyl- or ethyl ether, methoxy, ethoxy or Butoxytriglykol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and Mixtures of these solvents. The proportion by weight of these organic solvents in the total weight of cleaning agents according to the invention is in particular from 0.5 to 5.0

Wt .-%. A particularly preferred organic solvent which is particularly effective in stabilizing the detergents is glycerin and 1,2-propylene glycol. Liquid detergents containing at least one polyol, preferably from the group of glycerol and 1,2-propylene glycol wherein the weight proportion of the polyol in the total weight of the cleaning agent is preferably 0.1 and 10 wt .-%, preferably 0.2 and 8.0 wt .-% and in particular 0.5 and 5.0 wt .-%, are preferred according to the invention.
Other preferred organic solvents are the organic amines and alkanolamines. The cleaning agents according to the invention preferably contain these amines in amounts of from 0.1 to 10% by weight, preferably from 0.2 to 8.0% by weight and in particular from 0.5 to 5.0% by weight, in each case on her total weight. A particularly preferred alkanolamine is the ethanolamine.

Another preferred ingredient of the detergents of the invention is a sugar alcohol (alditol). The group of alditols includes noncyclic polyols of the formula HOCH ₂ [CH (OH)] _n CH ₂ OH. The alditols include, for example, mannitol (mannitol), isomalt, lactitol, sorbitol (sorbitol) and xylitol (xylitol), threitol, erythritol and arabitol. As particularly advantageous in terms of enzyme stability, the sorbitol has been found. The weight proportion of the sugar alcohol in the total weight of the cleaning agent is preferably 1.0 to 10 wt .-%, preferably 2.0 to 8.0 wt .-% and in particular 3.0 to 6.0 wt .-%.

• a) mindestens eine Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO. 1 angegebenen Aminosäuresequenz über deren Gesamtlänge zu mindestens 80% identisch ist und in der Zählung gemäß SEQ ID NO. 1 an Position 99 die Aminosäure Glutaminsäure (E) aufweist;
• b) 4-Formylphenylboronsäure
• c) mindestens ein weiteres, von der Protease a) verschiedenes Enzym,
• d) 10 bis 84,9 Gew.-% Gerüststoff(e);
• e) 15 bis 89,9 Gew.-% Wasser; enthält und
  die Zusammensetzung B
• m) 10 bis 75 Gew.% Gerüststoff(e);
• n) 25 bis 90 Gew.-% Wasser;
  enthält.

Liquid detergents according to the invention are preferably made up in multiphase form, that is to say by combining two or more separate, different liquid cleaning agents. This type of packaging increases the stability of the cleaning agent and improves its cleaning performance. A cleaning agent preferred according to the invention is characterized in that it comprises a packaging means and two separate liquid cleaning agents A and B contained in this packaging means, the composition A

• a) at least one protease which comprises an amino acid sequence which corresponds to the amino acid sequence shown in SEQ ID NO. 1 is at least 80% identical over its entire length and in the count according to SEQ ID NO. 1 at position 99 has the amino acid glutamic acid (E);
• b) 4-formylphenylboronic acid
• c) at least one further enzyme different from the protease a),
• d) from 10 to 84.9% by weight of builder (s);
• e) 15 to 89.9% by weight of water; contains and
  the composition B
• m) 10 to 75% by weight of builder (s);
• n) 25 to 90% by weight of water;
  contains.

The composition of some preferred cleaning agents can be found in the following tables (data in% by weight based on the total weight of the cleaning agent, unless stated otherwise). formula 1 Formula 2 Formula 3 Formula 4 Formula 5 Protease a) * 0.005 to 1.0 0.01 to 0.5 0.02 to 0.2 0.06 0.17 4-FPBA 0.0005 to 2.0 0.001 to 1.0 0.01 to 0.1 0.02 0.04 Enzyme c) ** 0.0005 to 1.0 0.001 to 0.5 0.002 to 0.2 0,004 0,012 Misc add 100 add 100 add 100 add 100 add 100 Protease according to claim 1, feature a)
** from the protease a) different enzyme Formula 6 Formula 7 Formula 8 Formula 9 Formula 10 Protease a) * 0.005 to 1.0 0.01 to 0.5 0.02 to 0.2 0.06 0.17 4-FPBA 0.0005 to 2.0 0.001 to 1.0 0.01 to 0.1 0.02 0.04 amylase 0.0005 to 1.0 0.001 to 0.5 0.002 to 0.2 0,004 0,012 Misc add 100 add 100 add 100 add 100 add 100 Protease according to claim 2 Formula 11 Formel12 Formula 13 Formula 14 Formula 15 Protease a) * 0.005 to 1.0 0.01 to 0.5 0.02 to 0.2 0.06 0.17 4-FPBA 0.0005 to 2.0 0.001 to 1.0 0.01 to 0.1 0.02 0.04 amylase 0.0005 to 1.0 0.001 to 0.5 0.002 to 0.2 0,004 0,012 water > 40 50 to 85 60 to 80 64 71 Misc add 100 add 100 add 100 add 100 add 100 Protease according to claim 2 Formula 16 Formula 17 Formula 18 Formula 19 Formula 20 Protease a) * 0.005 to 1.0 0.01 to 0.5 0.02 to 0.2 0.06 0.17 4-FPBA 0.0005 to 2.0 0.001 to 1.0 0.01 to 0.1 0.02 0.04 amylase 0.0005 to 1.0 0.001 to 0.5 0.002 to 0.2 0,004 0,012 builder 5.0 to 40 10 to 30 12 to 25 26 18 water > 40 50 to 85 60 to 80 64 71 Misc add 100 add 100 add 100 add 100 add 100 Protease according to claim 2 Formula 21 Formula 22 Formula 23 Formula 24 Formula 25 Protease a) * 0.005 to 1.0 0.01 to 0.5 0.02 to 0.2 0.06 0.17 4-FPBA 0.0005 to 2.0 0.001 to 1.0 0.01 to 0.1 0.02 0.04 amylase 0.0005 to 1.0 0.001 to 0.5 0.002 to 0.2 0,004 0,012 nonionic surfactant 0.2 to 10 0.4 to 7.0 0.6 to 6.0 4.0 2.0 water > 40 50 to 85 60 to 80 64 71 Misc add 100 add 100 add 100 add 100 add 100 Protease according to claim 2 Formula 26 Formula 27 Formula 28 Formula 29 Formula 30 Protease a) * 0.005 to 1.0 0.01 to 0.5 0.02 to 0.2 0.06 0.17 4-FPBA 0.0005 to 2.0 0.001 to 1.0 0.01 to 0.1 0.02 0.04 amylase 0.0005 to 1.0 0.001 to 0.5 0.002 to 0.2 0,004 0,012 builder 5.0 to 40 10 to 30 12 to 25 26 18 nonionic surfactant 0.2 to 10 0.4 to 7.0 0.6 to 6.0 4.0 2.0 water > 40 50 to 85 60 to 80 64 71 Misc add 100 add 100 add 100 add 100 add 100 Protease according to claim 2 Formula 31 Formula 32 Formula 33 Formula 34 Formula 35 Protease a) * 0.005 to 1.0 0.01 to 0.5 0.02 to 0.2 0.06 0.17 4-FPBA 0.0005 to 2.0 0.001 to 1.0 0.01 to 0.1 0.02 0.04 amylase 0.0005 to 1.0 0.001 to 0.5 0.002 to 0.2 0,004 0,012 Pentapotassium 5.0 to 40 10 to 30 12 to 25 18 12 HEDP 0.1 to 8.0 0.2 to 5.0 0.5 to 3.0 3.0 2.0 Sulfo copolymer 0.1 to 15 1.0 to 12 2.0 to 10 4.0 6.0 hydroxy mixed 0.2 to 10 0.4 to 7.0 0.6 to 6.0 4.0 2.0 water > 40 50 to 85 60 to 80 64 71 Misc add 100 add 100 add 100 add 100 add 100 Protease according to claim 2

A second subject of the present application is a purification process using one of the above-described cleaning agents according to the invention. In a preferred embodiment of the process according to the invention, the cleaning agent is introduced in the course of the process into an aqueous cleaning liquor.

A preferred cleaning process is a machine dishwashing process. The dosage of the cleaning agent according to the invention in the cleaning liquor can be done in such a method, for example by means of the metering chamber in the door or by means of an additional dosing in the interior of the dishwasher. Alternatively, the cleaning agent can also be applied directly to the soiled dishes or to one of the inner walls of the dishwasher, for example the inside of the door.

The implementation of the method according to the invention takes place in the interior of a commercial dishwasher. The cleaning program can be selected and determined in a dishwasher usually before the dishwashing process by the consumer. The cleaning program of the dishwasher used in the method according to the invention comprises at least one prewash cycle and one cleaning cycle. Cleaning programs which include further cleaning or rinsing cycles, for example a rinse cycle, are preferred according to the invention. The process according to the invention is particularly preferably part of a cleaning program, comprising a prewash cycle, a cleaning cycle and a rinse cycle. The inventive method is preferably used in conjunction with such cleaning programs in which the wash liquor is heated in the course of the cleaning cycle. In a preferred embodiment of the method according to the invention, the cleaning cycle, in the course of which the detergent according to the invention is metered into the interior of the dishwasher, is characterized in that in its course the temperature of the cleaning liquor is above 30 ° C., preferably above 40 ° C. and especially above 50 ° C increases.

Preferred embodiments of the automatic dishwashing process according to the invention result mutatis mutandis from the previous description of preferred embodiments of the detergent according to the invention, to which reference is made to avoid repetition at this point.

1. a) mindestens eine Protease, die eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO. 1 angegebenen Aminosäuresequenz über deren Gesamtlänge zu mindestens 95% identisch ist und in der Zählung gemäß SEQ ID NO. 1 an Position 99 die Aminosäure Glutaminsäure (E) aufweist;
   sowie
2. b) mindestens ein weiteres von der Protease a) verschiedenes Enzym, vorzugsweise mindestens eine weitere Amylase, und
3. c) mindestens ein organisches Lösungsmittel, wobei der Gewichtsanteil des mindestens einen organischen Lösungsmittels am Gesamtgewicht des Reinigungsmittels 0,5 bis 5,0 Gew.-% beträgt,

zur Steigerung der enzymatischen Reinigungsleistung, vorzugsweise der amylolytischen Reinigungsleistung des Reinigungsmittels.A third object of the present application is the use of 4-formylphenylboronic acid in detergents containing

1. a) at least one protease which comprises an amino acid sequence which corresponds to the amino acid sequence shown in SEQ ID NO. 1 amino acid sequence is at least 95% identical over the entire length and in the count according to SEQ ID NO. 1 at position 99 has the amino acid glutamic acid (E);
   such as
2. b) at least one other of the protease a) different enzyme, preferably at least one further amylase, and
3. c) at least one organic solvent, wherein the proportion by weight of the at least one organic solvent in the total weight of the cleaning agent is from 0.5 to 5.0% by weight,

to increase the enzymatic cleaning performance, preferably the amylolytic cleaning performance of the cleaning agent.

The use according to the invention is preferably carried out for the removal of amylase-sensitive stains on textiles or hard surfaces. It is particularly preferred to use the cleaning agent according to the invention as machine dishwashing detergent.

Example: Determination of the cleaning performance of automatic dishwashing detergents according to the invention

The basic formulation used was a two-phase liquid automatic dishwashing detergent of the following composition (all figures in percent by weight):
(a) Enzyme phase: Builder 18.0 sugar alcohol 12.0 Nonionic surfactant (C8-C10 fatty alcohol ethoxylate with 22 EO) 5.0 Alkaline compound (base) 3.5 boric acid 3.0 Phosphonate (HEDP) 1.5 Amylase preparation 1.5 Protease preparation 3.5 4-FPBA 0.02 Ca salt 1.2 Zn salt 0.2 thickener 1.0 Dye, perfume, preservative 0.3 water ad 100
(b) Alkaline phase: Builder 12.0 sodium 10.0 sulfopolymer 7.0 Alkaline compound (base) 4.0 Monoethanolamine 3.5 Phosphonate (HEDP) 4.0 thickener 1.0 Dye, perfume, preservative 0.3 water ad 100

• V1: Savinase Ultra 16 L (Novozymes)
• E1: Protease, die eine Aminosäuresequenz aufweist, die in der Zählung gemäß SEQ ID NO. 1 in den Positionen 1-98 und 100-269 SEQ ID NO. 1 entspricht und an Position 99 die Aminosäure Glutaminsäure (E) aufweist;

The enzyme phase of the base formulation was in each case mixed with 3.5% by weight of preparations of the following proteases for the various experimental procedures:

• V1: Savinase Ultra 16 L (Novozymes)
• E1: Protease which has an amino acid sequence which is counted in accordance with SEQ ID NO. 1 in positions 1-98 and 100-269 SEQ ID NO. 1 and at position 99 has the amino acid glutamic acid (E);

To determine the cleaning performance, both phases were dosed in equal parts (in each case 20 g per phase). Was washed in a pH range between pH 9 and pH 10 in a dishwasher G698SC the company Miele in a volume of 5 liters for a period of 60 minutes at a temperature of 50 ° C. Dishes containing oatmeal stains were used.

The evaluation of the cleaning performance is according to the standard IKW method visually on a scale from 1 to 10, with the value 10 is the best grade (no discernible residue). The results are summarized in Table 1 below: Table 1: IKW-Note V1 6.5 E1 7.3

The test series shows that the composition E1 according to the invention has a significantly improved amylolytic cleaning performance compared to the comparison formulation of the prior art.

SEQUENCE LISTING

• <110> Henkel AG & Co. KGaA
• <120> detergents or cleaners with improved enzyme performance
• <130> PT031510PCT
• <150> DE 102012215642
  <151> 2012-09-04
• <160> 3
• <170> PatentIn version 3.5
• <210> 1
  <211> 269
  <212> PRT
  <213> Bacillus lentus
• <400> 1
  
  
• <210> 2
  <211> 269
  <212> PRT
  <213> Bacillus lentus
• <400> 2
  
  
• <210> 3
  <211> 269
  <212> PRT
  <213> Bacillus lentus
• <400> 3
  
  

Claims (7)

1. A cleaning agent, containing

   a) at least one protease that has an amino acid sequence which is at least 95% identical over the total length thereof to the amino acid sequence specified in SEQ ID NO. 1 and has the amino acid glutamic acid (E) at position 99 using the numbering according to SEQ ID NO. 1;

   b) 4-formylphenylboronic acid,

   c) at least one further enzyme that is different from the protease a) and is from the group of amylases, and

   d) at least organic solvent, wherein the weight proportion of the at least one organic solvent with respect to the total weight of the cleaning agent is 0.5 to 5.0 wt.%.
2. The cleaning agent according to claim 1, characterized in that the protease a1) has an amino acid sequence which corresponds to SEQ ID NO. 1 in the positions 1-98 and 100-269 using the numbering according to SEQ ID NO. 1 and has the amino acid glutamic acid (E) at position 99.
3. The cleaning agent according to one of the preceding claims, characterized in that the weight proportion of the protease with respect to the total weight of the cleaning agent is 0.005 to 1.0 wt.%, preferably 0.01 to 0.5 wt.% and in particular 0.02 to 0.2 wt.%, based on active protein.
4. The cleaning agent according to one of the preceding claims, characterized in that the weight proportion of 4-formylphenylboronic acid with respect to the total weight of the cleaning agent is 0.0005 to 2.0 wt.%, preferably 0.001 to 1.0 wt.% and in particular 0.01 to 0.1 wt.%.
5. The cleaning agent according to one of the preceding claims, characterized in that the weight proportion of the enzyme c) with respect to the total weight of the cleaning agent is 0.0005 to 1.0 wt.%, preferably 0.001 to 0.5 wt.% and in particular 0.002 to 0.2 wt.%, based on active protein.
6. A cleaning method using a cleaning agent according to one of claims 1 to 5.
7. The use of 4-formylphenylboronic acid in cleaning agents, containing

   a) at least one protease that has an amino acid sequence which is at least 95% identical over the total length thereof to the amino acid sequence specified in SEQ ID NO. 1 and has
   the amino acid glutamic acid (E) at position 99 using the numbering according to SEQ ID NO. 1;
   and

   b) at least one further enzyme that is different from the protease a), preferably at least one further amylase, and

   c) at least organic solvent, wherein the weight proportion of the at least one organic solvent with respect to the total weight of the cleaning agent is 0.5 to 5.0 wt.%.

   for enhancing the enzymatic cleaning performance, preferably the amylolytic cleaning performance of the cleaning agent.